Trimethylsilylacetylene → 2-Bromo-5-trimethylsilanylethynyl-pyrazine

HRID 341233Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 341233
[Br:1][C:2]1[CH:7]=[N:6][C:5](I)=[CH:4][N:3]=1.[C:9]([Si:11]([CH3:14])([CH3:13])[CH3:12])#[CH:10]>CN(C=O)C.CCN(CC)CC.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[CH:7]=[N:6][C:5]([C:10]#[C:9][Si:11]([CH3:14])([CH3:13])[CH3:12])=[CH:4][N:3]=1

Komponenten

6

Edukt 2

HCID 66111TrimethylsilylacetyleneHCID 219312002-Bromo-5-iodopyrazine

Produkt 1

HCID 574976862-Bromo-5-trimethylsilanylethynyl-pyrazineAusbeute 83,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 22056947triethylamine N,N-dimethylformamideLösungsmittel

Versuchsvorschrift

A mixture of 2-bromo-5-iodo-pyrazine (1.14 g, 4.0 mmol) and copper (I) iodide (80 mg, 0.42 mmol) in DMF/Et3N (2:1, 24 ml) was deoxygenated by evacuate/refill with nitrogen (×3). Ethynyl-trimethyl-silane (680 μl, 4.8 mmol) followed by Pd(PPh3)4 (230 mg, 0.2 mmol) were added and the mixture was deoxygenated again (×1). The reaction was stirred at RT for 16 hours, then partitioned between Et2O/H2O. The organic layer was washed with water (×1), brine (×1), then dried (MgSO4), filtered and evaporated. The residue was purified by chromatography on silica (2∝34% Et2O/Petrol) to give the title compound (850 mg, waxy solid) as ˜3:1 mixture of mono coupled product to bis coupled. 1H NMR (400 MHz, CDCl3): 8.63 (1H, d), 8.43 (1H, d), 0.25 (9H, s), [Bis coupled product: 8.60 (s), 0.25 (s)] This material was used without further purification.

Aufarbeitung

  1. customwas deoxygenated
  2. customby evacuate/refill with nitrogen (×3)
  3. additionwere added
  4. customthe mixture was deoxygenated again (×1)
  5. custompartitioned between Et2O/H2O
  6. washThe organic layer was washed with water (×1), brine (×1)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by chromatography on silica (2∝34% Et2O/Petrol)

Quellen und Nachweise

ORD-Eintrag
ord-6733c57fcf1a48f990d43570573e519d
Quelldatensatz
uspto-grants-2014_11
Patentnummer
US08895745B2

Notizen zur Reaktion

Wird geladen…